Abstract
The mechanism of crystalline cellulose fragmentation has been debated between classical models proposing end-chain or intrachain scission to form short-chain (molten) anhydro-oligomer mixtures and volatile organic compounds. Models developed over the last few decades suggest global kinetics consistent with either mechanism, but validation of the chain-scission mechanism via measured reaction rates of cellulose has remained elusive. To resolve these differences, we introduce a new thermal-pulsing reactor four orders of magnitude faster than conventional thermogravimetic analysis (106 vs 102 °C/min) to measure the millisecond-resolved evolution of cellulose and its volatile products at 400-550 °C. By comparison of cellulose conversion and furan product formation kinetics, both mechanisms are shown to occur with the transition from chain-end scission to intrachain scission above 467 °C concurrent with liquid formation comprised of short-chain cellulose fragments.
Original language | English (US) |
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Pages (from-to) | 3108-3114 |
Number of pages | 7 |
Journal | Chemistry of Materials |
Volume | 28 |
Issue number | 9 |
DOIs | |
State | Published - May 10 2016 |
Bibliographical note
Publisher Copyright:© 2016 American Chemical Society.